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EP0311432A2 - Feuille stratifiée ayant des propriétés de barrière aux gaz - Google Patents

Feuille stratifiée ayant des propriétés de barrière aux gaz Download PDF

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Publication number
EP0311432A2
EP0311432A2 EP88309388A EP88309388A EP0311432A2 EP 0311432 A2 EP0311432 A2 EP 0311432A2 EP 88309388 A EP88309388 A EP 88309388A EP 88309388 A EP88309388 A EP 88309388A EP 0311432 A2 EP0311432 A2 EP 0311432A2
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EP
European Patent Office
Prior art keywords
film
gas barrier
laminated
silicon oxide
thickness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88309388A
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German (de)
English (en)
Other versions
EP0311432A3 (en
EP0311432B1 (fr
Inventor
Tsutomu Sawada
Shinichi Ohashi
Shigenobu Yoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Kasei Polytec Co
Mitsubishi Monsanto Chemical Co
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Filing date
Publication date
Priority claimed from JP62252722A external-priority patent/JPH0822580B2/ja
Priority claimed from JP63007977A external-priority patent/JPH0632921B2/ja
Priority claimed from JP63185113A external-priority patent/JPH0234328A/ja
Application filed by Mitsubishi Kasei Polytec Co, Mitsubishi Monsanto Chemical Co filed Critical Mitsubishi Kasei Polytec Co
Publication of EP0311432A2 publication Critical patent/EP0311432A2/fr
Publication of EP0311432A3 publication Critical patent/EP0311432A3/en
Application granted granted Critical
Publication of EP0311432B1 publication Critical patent/EP0311432B1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a laminated thermoplastic film having excellent gas barrier properties. More particularly, it relates to a laminated plastic film which has a high gas barrier property against steam and oxygen as well as transparency and is suitable for a variety of packaging materials.
  • Plastic films and their molded pieces used for packaging materials of foods, pharmaceuticals, chemicals and the like are made of gas barrier materials which are impermeable to gases such as steam, oxygen or the like in order to prevent the change of properties of a packaged content.
  • gases such as steam, oxygen or the like
  • materials which have been additionally laminated with a metal foil such as aluminium or the like or on which metal such as aluminum or the like has been deposited are used.
  • Films made of a polyvinylidene chloride or a vinylidene chloride type resin such as a copolymer of vinylidene chloride as a main component and other monomers copolymerizable with vinylidene chloride such as vinyl chloride, methyl acrylate, methyl methacrylate, acrylonitrile or the like or vinylidene chloride type resin coated films in which films made of polypropylene, polyester, polyamide or the like have been coated with the vinylidene chloride type resin are also known as packaging materials having gas barrier properties.
  • a polyvinyl alcohol type resin such as polyvinyl alcohol or an ethylene-vinyl alcohol copolymer is also a material excellent in oxygen barrier properties.
  • the polyvinyl alcohol type resin is inferior in steam barrier properties, and oxygen barrier properties are also deteriorated under a high humidity.
  • a steam barrier resin film made of polypropylene, polyethylene, polyester or the like has been laminated on the polyvinyl alcohol type resin film.
  • conventional vinylidene chloride type resin films and polyvinyl alcohol type resin films can be formed transparent, but these films are not satisfactory in gas barrier properties to steam and oxygen.
  • the thickness of the films must be increased. However, if the thickness of the films is increased, the transparency or softness will be impaired. Accordingly, these films are inadequate to packaging materials which require a high level of gas barrier properties.
  • a packaging material that a metal oxide film is deposited on a plastic film to afford gas barrier properties is also insufficient for gas barrier properties. Accordingly, it is unsatisfactory for the use which requires a high level of gas barrier properties.
  • the present invention has been done on the basis of the aforementioned background, and the object of the present invention is to provide a gas barrier laminated plastic film which has a high level of gas barrier properties without increasing the thickness of the film and can exhibit excellent transparency.
  • the gas barrier laminated film according to the present invention comprises a thermoplastic film having a polar group and a thin layer of silicon oxide formed on the one side of the thermoplastic film, in which the bond energy of silicon in the silicon oxide of the layer varies along the direction of the thickness of the layer and has a large value in the vicinity of the plastic film.
  • thermoplastic film there can be used as a thermoplastic film a polyvinyl alcohol film which has a saponification value of 99% or more and has been stretched monoaxially five folds or more.
  • thermoplastic film there can be used as a thermoplastic film a stretched polyvinyl alcohol film which has a saponification value of 99% or more and the dimensional variation rate of 20/0 or less at the temperature of 120° C.
  • the thin layer of silicon oxide can be formed by any one of a vacuum deposition method, a spattering method or an ion plating method.
  • a further plastic layer can be laminated on the surface of the film layer.
  • the bond energy of silicon is large in the vicinity of the bonding portion of the thermoplastic film having a polar group and the silicon oxide layer. This indicates that the surface of the thermoplastic film and the thin layer are strongly bonded and that the network of atoms at the strong bonding portion makes gas molecules such as water molecules or oxygen molecules substantially less permeable and thus exhibits excellent gas barrier properties. This explanation is proposed for the better understanding of the present invention and does not intend to limit the scope of the present invention.
  • the present invention has following effects as will be illustrated in the following examples.
  • the gas barrier laminated plastic film according to the present invention has an extremely high level of gas barrier properties without increasing the thickness of the film and can exhibit an excellent transparency. It also has a softness and is excellent in strength and economy.
  • the gas barrier laminated plastic film according to the present invention can be used as a packaging material for foods, pharmaceuticals, chemicals or the like, and it can also be applied to packaging which requires a high level of gas barrier properties. Thus, it can be used for applications over a wide range and has a large usefulness in industry.
  • a plastic layer is further formed in lamination, and thus it is possible to exhibit more excellent gas barrier properties by further lowering the moisture permeability.
  • thermoplastic film having a polar group such as a hydroxyl, e.g. a polyvinyl alcohol type film, is used, so that if a thin layer of silicon oxide is formed on this film by a vacuum deposition method or the like, the polar group of the plastic film and the silicon oxide interact at an initial stage of the formation to give a larger bond energy of silicon in the vicinity of the plastic film.
  • a film which exhibits excellent gas barrier properties there can be obtained a film which exhibits excellent gas barrier properties.
  • a stretched polyvinyl alcohol film more preferably a stretched polyvinyl alcohol film having a dimensional stability even at high temperature is used, a transparent laminated plastic film having an extremely excellent strength can be obtained.
  • a thin layer of silicon oxide which is formed on the one side of a thermoplastic film having a polar group has a large bond energy of silicon in the vicinity of the bonding portion to the thermoplastic film.
  • thermoplastic film which the bond energy of silicon in the vicinity of a thermoplastic film is lesser than or same as that in the central portion or the surface portion which does not bond to the thermoplastic film will not improve the gas barrier properties sufficiently.
  • bond energy of silicon in the silicon oxide means the bond energy of Si2p measured by the ESCA (Electron Spectroscopy for Chemical Analysis) method.
  • the bond energy of silicon Si2p in the direction of the thickness of thin silicon oxide layer can be measured by the ESCA method with etching the exposed layer with an argon ion or the like.
  • the bond energy of silicon in the vicinity of the thermoplastic film is desirably 0.3 eV or more, preferably 0.5 eV or more larger than that in the central portion and the surface portion of the thin layer which are out of contact with the thermoplastic film.
  • the thin layer of silicon oxide can be formed by depositing on the surface of a plastic film by either method of the vacuum deposition method, the spattering method or the ion plating method with the use of a deposition material such as silicon monoxide, silicon dioxide or a mixture thereof.
  • silicon monoxide or silicon dioxide is used as a deposition material and vaporized with heating under a vacuum of 10- 3 to 10- 5 Torr by heating with such a method as electron beam heating, high frequency induction heating or resistance heating.
  • the method for forming the thin layer is not limited to those described above, and a variety of methods can be applied.
  • the reaction deposition method which is conducted with the use of deposition materials such as silicon, silicon monoxide, silicon dioxide or a mixture thereof with supplying oxygen gas.
  • the plastic film as a film to be deposited may be the one which has been subjected to final setting treatment or the one which has been subjected to only one step of the thermal setting treatment. In the latter case, the plastic film is placed in a deposition chamber and subjected to the second thermal setting treatment to afford dimensional stability prior to deposition, and then the film is subjected to deposition treatment.
  • the thin layer of silicon oxide formed on the thermoplastic film has a thickness of 3 to 700 nm, preferably 5 to 500 nm. This is because the gas barrier properties is insufficient at the thickness of the thin layer of less than 5 nm, an its tendency becomes striking at the thickness of less than 3 nm; on the other hand, the thin layer may warp or the thin layer may be cracked or separated to impair the flexibility at the thickness exceeding 500 nm, and its tendency becomes striking at the thickness exceeding 700 nm.
  • additives can be included appropriately according to the necessity. If the amount of the additives is maintained at the level of 100/0 by weight or less, the contamination of calcium, magnesium or an oxide thereof as impurities will not affect deleteriously the layer.
  • the plastic film used in the present invention is a thermoplastic having a polar group which can deposit and bond the thin layer of silicon oxide and the thermoplastic film so that the bond energy of silicon becomes large in the vicinity of the two.
  • thermoplastic film having a polar group is a polyvinyl alcohol type resin such as polyvinyl alcohol, an ethylene-vinyl alcohol copolymer film or the like; and a polyvinyl acetal type resin such as polyvinyl formal, polyvinyl butyral or the like.
  • the polyvinyl alcohol used in the present invention is desirably the one having a saponification value of 99% or more. This is because the improvement of the gas barrier properties cannot be much expected at a saponification value of less than 990/0.
  • the size or shape of the thermoplastic film is selected appropriately.
  • the film may be any one of the unstretched or stretched monoaxially or biaxially.
  • a polyvinyl alcohol type resin is used, a polyvinyl alcohol having been stretched at least monoaxially at a stretch ratio of 5 or more is desirable.
  • the film may be the one which is stretched monoaxially or biaxially. It is not limited to a film which has been stretched in one step and may be the one having been stretched in multi-steps if the stretch ratio is in the range where the total stretch ratio is 5 or more.
  • the plastic film used in the present invention is preferably a stretched polyvinyl alcohol film having a dimensional variation rate of 2% or less at a temperature of 120° C. If the dimensional variation rate exceeds 20/0, the gas barrier properties will not be improved appreciably even though the thin layer of silicon oxide is formed on the surface of the plastic film by the vacuum deposition method, the spattering method or the ion plating method. The mechanism being ambiguous can be presumed that the polyvinyl alcohol film is heated on the formation of the thin layer and is shrinked or expanded to change its dimension, and if the dimensional variation rate exceeds 20/0, cracking, uneven thickness or pinhole is generated in the thin layer of the silicon oxide and thus a uniform dense thin layer will not be obtained.
  • the polyvinyl alcohol is stretched and then set thermally at a temperature from its glass transition point to its melting point, so that the crystallinity is increased and the orientation of the molecular chain is set.
  • the thermal setting operation can be performed in one step or in multi-step. When performed in two steps, the thermal setting in the latter step is preferably conducted at a temperature of 120°C or less.
  • the thermal setting operation in the latter step it is possible to use a method that a stretched film is moistened under a high humidity condition, an orientation stress is relaxed in the plasticized state, and the moisture having been absorbed in the film is removed by drying with heating.
  • thermoplastic film on which the thin layer of silicon oxide has a thickness of 5 to 400 ⁇ m, preferably 10 to 200 ⁇ m.
  • the silicon oxide layer on the one surface of which a plastic layer is laminated can be further laminated the same or different plastic layer.
  • the laminating method there is a method that a plastic layer is laminated on the surface of the silicon oxide layer or a plastic layer is coated on the surface of the silicon oxide layer.
  • the plastic layer used for lamination is not critical, but it is preferably a layer which has a moisture permeability of 50 g/m 2 ⁇ 24 hr measured under the conditions of the temperature of 40°C and the relative humidity of 900/0 in accordance with ASTM F372.
  • the thickness can be selected in the range of 5 to 400 ⁇ m.
  • an olefin resin such as polyethylene and an ethylene type copolymer, and polypropylene and a propylene type copolymer
  • a polyvinyl chloride type resin such as polyvinyl chloride and a copolymer thereof
  • a polyvinylidene chloride such as polyvinylidene chloride and a copolymer thereof
  • a polyester resin such as polyethylene terephthalate or the like
  • a fluorine resin such as polytetrafluoroethylene or the like
  • a coated film that one of the resin films specified above is coated with the other resin such as a polyvinylidene chloride type resin.
  • These resin film may be any one of the unstretched or the stretched monoaxially or biaxially.
  • the coating agent suitably used is preferably a solution or a dispersion of a polyvinylidene type resin such as polyvinylidene chloride and a copolymer thereof, a polyester resin such as polyethylene terephthalate and the like, and a fluorine resin such as polytetrafluoroethylene and the like.
  • an anchor-coat can be used in order to enhance the adhesion strength of the coating and the thin layer.
  • adhesion promoters of the isocyanate type, the polyethyleneimine type, the organotitanium type or the like and adhesives of the polyurethane type, the polyester type or the like there can be mentioned adhesion promoters of the isocyanate type, the polyethyleneimine type, the organotitanium type or the like and adhesives of the polyurethane type, the polyester type or the like.
  • a substance which enhances heat-sealing properties of the film can be coated or laminated on the surface of the thin layer, the surface of the plastic layer, the surface of the plastic coating or both the surfaces according to its usage.
  • the substance for enhancing the heat-sealing properties there are, for example, a low density polyethylene, an ethylene-vinyl acetate copolymer, a polypropylene, an ionomer and the like.
  • thermoplastic film polyvinyl alcohol film
  • bond energy of silicon (Si2p) of the thin layer the moisture permeability of the laminated film obtained
  • oxygen permeability the transparency
  • the thickness of the thin layer of silicon oxide is measured by a rock crystal film thickness meter.
  • a sample piece of a square having a side length of 120 mm was prepared from the film and conditioned under the atmosphere at the temperature of 23° C and the relative humidity of 500/0 for 24 hours, and then a line in the shape of a square having a side length of 100 mm was marked on the sample piece. It was placed in the constant temperature air bath adjusted at a temperature of 120° C, taken out from the bath after 5 minutes and conditioned at the atmosphere at the temperature of 23° C and the relative humidity of 500/0 for 24 hours, and then the absolute value of the variation of the distance of the square mark line ( ⁇ 1 : mm) was measured to obtain the dimensional variation rate by calculating from the following equation:
  • a transparent gas barrier laminated film was obtained by evaporating by heating silicon monoxide (SiO) having a purity of 99.9% under a vacuum of 5x10- 5 Torr and forming a thin silicon oxide layer of a thickness of 100 nm silicon oxide on the one side of a polyvinyl alcohol film having a saponification value of 99.9% (stretch ratio: 5, monoaxially stretched, thickness: 20 ⁇ m).
  • SiO silicon monoxide
  • the moisture permeability and the oxygen permeability were measured by the aforementioned methods, and the transparency was evaluated by a naked eye.
  • a thin layer of the silicon oxide was formed on the one side of the polyvinyl alcohol film in the same manner as in Example A1 except that a polyvinyl alcohol film having a saponification value of 99.9% and a stretch ratio of 3x3 was further stretched monoaxially to the stretch ratio of 3x8.7 to give a thickness of 25 ⁇ m.
  • evaluation tests were conducted for the same items as in Example A1. The results are specified in Table 1.
  • Laminated films were obtained in the same manner as in Example A1 except that the thicknesses of the thin layers of the silicon oxide formed on the one side of the polyvinyl alcohol film were made 50 nm (Example A3) and 200 nm (Example A4), respectively.
  • a laminated film was obtained by forming a thin layer of the silicon oxide having a thickness of 100 nm on the one side of the polyvinyl alcohol film in the same manner as in Example A1 except that a silicon dioxide having a purity of 99.9% was used instead of the silicon oxide having a purity of 99.9%.
  • Laminated films were obtained by forming a thin layer of silicon oxide having a thickness of 100 nm on the one side of the films in the same manner as in Example A1 except that the polyvinyl alcohol film was replaced by a biaxially stretched polyethylene terephthalate film (stretch ratio: 3x3) having a thickness of 25 ⁇ m (Comparative Example A1), a biaxially stretched polyvinyl alcohol film (stretch ratio: 3x3) having a saponification value of 99.9% and a thickness of 25 ⁇ m (Comparative Example A2) and a monoaxially stretched polyvinyl alcohol film (stretch ratio: 5) having a saponification value of 99.00/ 0 and a thickness of 20 ⁇ m (Comparative Example A3), respectively.
  • a biaxially stretched polyethylene terephthalate film having a thickness of 25 ⁇ m
  • stretch ratio: 3x3 having a saponification value of 99.9% and a thickness of 25 ⁇ m
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the deposited silicon oxide of the transparent gas barrier laminated film which had been formed in Example A1 a polypropylene film having a vinylidene chloride type resin coat layer (thickness: 10 ⁇ m) and a total thickness of 30 ⁇ m (stretch ratio: 5x5, moisture permeability: 1.2 g/m 2 ⁇ 24 hr, referred to hereinafter as "K-OPP") so that the vinylidene chloride type resin coat layer and the silicon oxide deposited surface are contacted through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the transparent gas barrier laminated film the moisture permeability and the oxygen permeability were measured and the transparency was evaluated by naked eyes.
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the polyvinyl alcohol of the transparent gas barrier laminated film which was obtained in Example A6 a low density polyethylene film (thickness: 40 ⁇ m) through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1
  • the moisture permeability and the oxygen permeability were measured and the transparency was evaluated by naked eyes.
  • a laminated film was obtained in the same manner as in Example A6 except that the K-OPP film laminated on the silicon oxide deposited surface of the transparent laminated film in Example A6 was replaced by a biaxially stretched polyethylene terephthalate film (stretch ratio: 3x3) having a thickness of 25 ⁇ m (moisture permeability: 20 g/m 2 ⁇ 24 hr).
  • a laminated film was obtained in the same manner as in Example A7 except that the laminated film obtained in Example A8 was used instead of the laminated film obtained in Example A6.
  • a laminated film was obtained in the same manner as in Example A6 except that the K-OPP film laminated on the silicon oxide deposited surface of the transparent laminated film obtained in Example A6 was replaced by a biaxially stretched nylon 6 film (stretch ratio: 3x3) having a thickness of 15 ⁇ m (moisture permeability: 150 g/m 2 •24 hr).
  • a laminated film was obtained in the same manner as in Example A7 except that the laminated film obtained in Example A10 was used instead of the laminated film obtained in Example A6.
  • Example A2 On the silicon oxide deposited surface of the transparent gas barrier laminated film obtained in Example A2 was coated in the first place as an anchor-coating an urethane type adhesive layer (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1) to form a coat layer having a thickness of 1 ⁇ m.
  • an urethane type adhesive layer manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1
  • a vinylidene type resin latex manufactured by Kureha Chemical Industry Co., Ltd.; KUREHARON LATEX DO-870
  • K film a transparent gas barrier laminated plastic film
  • the moisture permeability and the oxygen permeability were measured in the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified in Table 2.
  • a transparent gas barrier laminated plastic film was obtained by laminating on the silicon oxide deposited surface of the transparent gas barrier laminated film obtained in Example A2 the same K-OPP as used in Example A6 so that the vinylidene chloride type resin coat layer and the silicon oxide deposited surface and the surface of the polyvinyl alcohol film and a low density polyethylene film (thickness: 40 wm) were contacted respectively through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the moisture permeability and the oxygen permeability were measured and the transparency was evaluated by naked eyes.
  • a laminated film was obtained in the same manner as in Example A13 except that the laminated film obtained in Comparative Example A1 was used instead of the laminated film obtained in Example A2, wherein the low density polyethylene film was laminated on the surface of the polyethylene terephthalate.
  • the moisture permeability and the oxygen permeability were measured and the transparency was evaluated by naked eyes.
  • a polyviny l alcohol film having a dimensional variation rate of 0.8% in one direction and 0.6% in the longitudinal direction was prepared by subjecting a polyvinyl alcohol film having a saponification value of 99.9% (stretch ratio: 3x3, biaxially stretched, thickness: 25 ⁇ m) to a thermal setting treatment at a temperature of 210°C for 10 seconds.
  • a transparent gas barrier laminated film was obtained by evaporating by heating silicon monoxide (SiO) having a purity of 99.9% under a vacuum of 5x10- 5 Torr and forming a thin silicon oxide layer of a thickness of 100 nm on the one side of a polyvinyl alcohol film.
  • the moisture permeability and the oxygen permeability were measured by the aforementioned methods, and the transparency was evaluated by a naked eye.
  • a polyviny l alcohol film having a dimensional variation rate of 1.7% in one direction and 0.9% in the longitudinal direction was prepared by further subjecting a polyvinyl alcohol film having a saponification value of 99.9% (stretch ratio: 3x3, biaxially stretched, thickness: 25 ⁇ m) to a monoaxial stretching to a stretch ratio of 2.1 to give a total stretch ratio of 3x6.3, a two-step thermal setting treatment at a temperature of 200° C for 22 seconds and further at 80°C for 1.5 hours.
  • a transparent gas barrier laminated film was obtained by evaporating by heating silicon monoxide (SiO) having a purity of 99.9% under a vacuum of 5x10- 5 Torr and forming a thin silicon oxide layer of a thickness of 100 nm on the one side of a polyvinyl alcohol film.
  • SiO silicon monoxide
  • the moisture permeability and the oxygen permeability were measured by the aforementioned methods, and the transparency was evaluated by a naked eye.
  • a laminated film was obtained in the same manner as in Exampe B2 except that the same polyvinyl alcohol film as used in the above-described Example which had been subjected only to the thermal setting treatment at 200°C for 22 seconds was charged in a vacuum deposition chamber and then the second thermal setting treatment was conducted at 100°C for 5 minutes prior to the deposition operation (the dimensional variation rate of the film obtained being 0.4% in one direction and 0.30/0 in the vertical direction).
  • Laminated films were obtained in the same manner as in Example B3 except that the thickness of the transparent silicon oxide layer formed on the one side of the polyvinyl alcohol film was made 50 nm (Example B4) and 200 nm (Example B5), respectively.
  • a laminated film was obtained by forming on the one side of the polyvinyl alcohol film a thin silicon oxide layer of a thickness of 100 nm in the same manner as in Example B1 except that a biaxially stretched polyvinyl alcohol film having a saponification value of 90.0% was used instead of the biaxially stretched polyvinyl alcohol film having a saponification value of 99.0% used in the above-described Example.
  • a laminated film was obtained by forming on the one side of the polyvinyl alcohol film a thin silicon oxide layer of a thickness of 100 nm in the same manner as in Example B2 except that a polyvinyl alcohol film which had not been subjected to the second thermal treatment at 80°C for 1.5 minutes (the dimensional variation rate being 3.0% in one direction and 1.5% in the vertical direction) was used instead of the polyvinyl alcohol film which had been subjected to the two-step thermal setting treatment in the above-described Example.
  • the evaluation tests were conducted for the same items as in Example B2.
  • a laminated film was obtained by forming a thin layer of the silicon oxide having a thickness of 100 nm on the one side of the films in the same manner as in Example B1 except that the polyvinyl alcohol film used in said Example was replaced by a biaxially stretched polyethylene terephthalate film (stretch ratio: 3x3) having a thickness of 25 ⁇ m.
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the deposited silicon oxide of the transparent gas barrier laminated film which had been formed in Example B1 a polypropylene film having a vinylidene chloride type resin coat layer (thickness: 10 ⁇ m) and a total thickness of 30 ⁇ m (stretch ratio: 3x10, moisture permeability: 1.2 g/m 2 ⁇ 24 hr, referred to hereinafter as "K-OPP") so that the vinylidene chloride type resin coat layer and the silicon oxide deposited surface are contacted through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the transparent gas barrier laminated film the moisture permeability and the oxygen permeability were measured by the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the polyvinyl alcohol of the transparent gas barrier laminated film which was obtained in Example B6 an ethylene-vinyl acetate copolymer film (thickness: 40 ⁇ m) as a heat-sealing layer through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the moisture permeability and the oxygen permeability were measured by the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified in Table 4.
  • a laminated film in which the K-OPP had been laminated by adhesion was obtained in the same manner as in Example B6 except that the laminated film obtained in Example B1 and used in Example B6 was replaced by a laminated film obtained in Example B3.
  • a laminated film having been provided with a heat-sealing layer was obtained in the same manner as in Example B7 except that the laminated film obtained in Example B8 was used instead of the laminated film obtained in Example B6.
  • a laminated film was obtained in the same manner as in Example B8 except that the K-OPP film laminated on the silicon oxide deposited surface of the transparent laminated film obtained in Example B8 was replaced by a biaxially stretched polyethylene terephthalate film (stretch ratio: 3x3) having a thickness of 25 ⁇ m (moisture permeability: 20 g/m 2 e 24 hr).
  • a laminated film having been provided with a heat sealing layer was obtained in the same manner as in Example B7 except that the laminated film obtained in Example B10 was used instead of the laminated film obtained in Example B6.
  • a laminated film was obtained in the same manner as in Example B8 except that the K-OPP film laminated on the silicon oxide deposited surface of the transparent laminated film was replaced by a biaxially stretched nylon 6 film (stretch ratio: 3x3) having a thickness of 15 ⁇ m (moisture permeability: 150 g/m 2 ⁇ 24 hr).
  • evaluation tests were conducted for the same items as in Example B8.
  • a laminated film having been provided with a heat-sealing layer was obtained in the same manner as in Example B7 except that the laminated film obtained in Example B12 was used instead of the laminated film obtained in Example B6.
  • Example B3 On the silicon oxide deposited surface of the transparent gas barrier laminated film obtained in Example B3 was coated in the first place as an anchor-coating an urethane type adhesive layer (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1) to form a coat layer having a thickness of 111m.
  • an urethane type adhesive layer manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1
  • a vinylidene type resin latex manufactured by Kureha Chemical Industry Co., Ltd.; KUREHARON LATEX DO-870
  • K film moisture permeability: 1.2 g/m 2 ⁇ 24 hr
  • the moisture permeability and the oxygen permeability were measured in the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified in Table 4.
  • a transparent gas barrier laminated plastic film was obtained by laminating on the silicon oxide deposited surface of the transparent gas barrier laminated film obtained in Example B3 the same K-OPP as used in Example B6 so that the vinylidene chloride type resin coat layer and the silicon oxide deposited surface and the surface of the polyvinyl alcohol film and an ethylene-vinyl acetate copolymer film (thickness: 40 ⁇ m) were contacted respectively through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the moisture permeability and the oxygen permeability were measured and the transparency was evaluated by naked eyes.
  • a transparent gas barrier laminated film was obtained by evaporating by heating silicon monoxide (SiO) having a purity of 99.9% under a vacuum of 5x10- 5 Torr on the surface of a polyvinyl alcohol film having a saponification value of 99.9°/o (stretch ratio: 3x3, biaxially stretched, thickness: 12 ⁇ m) and forming a transparent thin silicon oxide layer of a thickness of 100 nm on the one side of a polyvinyl alcohol film.
  • SiO silicon monoxide
  • the bond energy of silicon (Si2p) of the silicon oxide film layer, the moisture permeability and the oxygen permeability were measured by the aforementioned methods, and the transparency was evaluated by a naked eye.
  • a thin silicon oxide layer was formed on the one side of an ethylene-vinyl alcohol copolymer in the same manner as in Example C1 except that the polyvinyl alcohol film having a saponification value of 99.9% was replaced by an ethylene-vinyl alcohol copolymer film (ethylene content: 32 moleO/o; stretch ratio: 3x3; biaxially stretched; thickness; 12 I lm).
  • a thin silicon oxide layer was formed on the one side of a polyethylene terephthalate film in the same manner as in Example C1 except that the polyvinyl alcohol film having a saponification value of 99.9% was replaced by a polyethylene terephthalate film (ethylene content: 32 mole O /o; stretch ratio: 3x3; biaxially stretched; thickness: 12 ⁇ m).
  • a thin silicon oxide layer was formed on the one side of a polypropylene film in the same manner as in Example C1 except that the polyvinyl alcohol film having a saponification value of 99.9% was replaced by a polypropylene film (stretch ratio: 3x10; biaxially stretched; thickness: 20 ⁇ m).
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the deposited silicon oxide of the transparent gas barrier laminated film which had been formed in Example C1 a polypropylene film (stretch ratio: 3x10; biaxially stretched; thickness: 20 ⁇ m; moisture permeability: 8 g/ M 2 o24 hr, referred to hereinafter as "OPP") through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENATE A-10 in a proportion of 9:1).
  • the moisture permeability and the oxygen permeability were measured by the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified in Table 6.
  • a transparent gas barrier laminated plastic film was obtained by laminating on the surface of the polyvinyl alcohol film of the above-described laminated film an ethylene vinyl acetate copolymer having a thickness of 40 ⁇ m as a heat-sealing layer through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the transparent gas barrier laminated film the moisture permeability and the oxygen permeability were measured by the methods described above and the transparency was evaluated by naked eyes. The results of the measurements are specified in Table 6.
  • a transparent gas barrier laminated plastic layer that the OPP had been adhered and laminated was obtained in the same manner as in Example C1 except that the transparent gas barrier laminated film obtained in Example C2 was used instead of the transparent gas barrier laminated film obtained in Example C1.
  • a transparent gas barrier laminated plastic layer was obtained in the same manner as in Example C3 except that the OPP film laminated on the silicon oxide deposited surface was replaced by a nylon 6 film (stretch ratio: 3x3, biaxially stretched, thickness: 15 IJ.m; moisture permeability: 150 g/m 2 ⁇ 24 hr).
  • a transparent laminated plastic layer was obtained by laminating on the surface of the deposited silicon oxide of the transparent gas barrier laminated film which had been formed in Comparative Example C1 the same OPP as used in foregoing Example 3 through an urethane type adhesive layer having a thickness of 2 ⁇ m (manufactured by Takeda Chemical Industries, Ltd., a two-component type adhesive comprising mixing TAKELAK A-606 and TAKENAT A-10 in a proportion of 9:1).
  • the moisture permeability and the oxygen permeability were measured by the methods described above and the transparency was evaluated by naked eyes.
  • a transparent laminated plastic film was obtained in the same manner as in Comparative Example C3 except that the plastic layer on which the silicon oxide layer had been deposited was replaced by the laminated film obtained in Comparative Example C2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
EP19880309388 1987-10-07 1988-10-07 Feuille stratifiée ayant des propriétés de barrière aux gaz Expired - Lifetime EP0311432B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP62252722A JPH0822580B2 (ja) 1987-10-07 1987-10-07 ガスバリヤ性の優れた透明プラスチックフィルム
JP252722/87 1987-10-07
JP63007977A JPH0632921B2 (ja) 1988-01-18 1988-01-18 ガスバリヤ性の優れた透明プラスチックフィルム
JP7977/88 1988-01-18
JP63185113A JPH0234328A (ja) 1988-07-25 1988-07-25 ガスバリヤ性積層フィルム
JP185113/88 1988-07-25

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EP0311432A2 true EP0311432A2 (fr) 1989-04-12
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FR2670506A1 (fr) * 1990-12-17 1992-06-19 Air Liquide Procede de depot d'une couche d'oxyde de silicium liee a un substrat en polyolefine.
EP0460796A3 (en) * 1990-04-20 1992-07-08 E.I. Du Pont De Nemours And Company Barrier materials useful for packaging
EP0640472A3 (fr) * 1993-08-25 1995-07-05 Toppan Printing Co Ltd Matériaux d'emballage ayant caractéristique de barrière à l'oxygène.
EP0703267A1 (fr) * 1994-08-25 1996-03-27 Agfa-Gevaert AG Articles faconnés contenant du polyacétylène
US5527629A (en) * 1990-12-17 1996-06-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process of depositing a layer of silicon oxide bonded to a substrate of polymeric material using high pressure and electrical discharge
EP0723860A1 (fr) * 1995-01-26 1996-07-31 Elf Atochem S.A. Matériau d'emballage comprenant une couche d'oxyde de silicium et une couche de polyoléfine
WO1997042029A1 (fr) * 1996-05-06 1997-11-13 Convenience Food Systems B.V. Feuilles d'arret multicouches scellables transparentes
WO1997047678A1 (fr) * 1996-06-12 1997-12-18 Hoechst Trespaphan Gmbh Procede d'application d'une couche de fond de revetements sur des articles de polyolefine
US5904952A (en) * 1987-07-15 1999-05-18 The Boc Group, Inc. Method of plasma enhanced silicon oxide deposition
US5925428A (en) * 1996-06-12 1999-07-20 Hoechst Trespaphan Gmbh Vapor barrier coating for polymeric articles
US6013128A (en) * 1996-06-12 2000-01-11 Hoechst Trespaphan Gmbh Vapor barrier coating for polymeric articles
US6086991A (en) * 1996-06-12 2000-07-11 Hoechst Trespaphan Gmbh Method of priming poly(ethylene terephthalate) articles for coating
US6254994B1 (en) 1996-06-12 2001-07-03 Hoechst Trespaphan Gmbh Method of priming polyolefin articles for coating
US6531197B2 (en) 1999-04-26 2003-03-11 Illinois Tool Works Desiccant barrier container
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DE102008019665A1 (de) 2008-04-18 2009-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Transparentes Barriereschichtsystem

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JP5889281B2 (ja) 2011-03-31 2016-03-22 三菱樹脂株式会社 バリア性蒸着フィルム
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Publication number Priority date Publication date Assignee Title
US5904952A (en) * 1987-07-15 1999-05-18 The Boc Group, Inc. Method of plasma enhanced silicon oxide deposition
EP0460796A3 (en) * 1990-04-20 1992-07-08 E.I. Du Pont De Nemours And Company Barrier materials useful for packaging
EP0469926A1 (fr) * 1990-08-03 1992-02-05 The Boc Group, Inc. Barrières de vapeur en couches minces à base d'oxyde de silicium
AU655188B2 (en) * 1990-08-03 1994-12-08 Valmet General Limited Silicon oxide based thin film vapor barriers
FR2670506A1 (fr) * 1990-12-17 1992-06-19 Air Liquide Procede de depot d'une couche d'oxyde de silicium liee a un substrat en polyolefine.
WO1992011312A1 (fr) * 1990-12-17 1992-07-09 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procede de depot d'une couche d'oxyde de silicium liee a un substrat en materiau polymere
US5527629A (en) * 1990-12-17 1996-06-18 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process of depositing a layer of silicon oxide bonded to a substrate of polymeric material using high pressure and electrical discharge
EP0640472A3 (fr) * 1993-08-25 1995-07-05 Toppan Printing Co Ltd Matériaux d'emballage ayant caractéristique de barrière à l'oxygène.
EP0703267A1 (fr) * 1994-08-25 1996-03-27 Agfa-Gevaert AG Articles faconnés contenant du polyacétylène
US5650227A (en) * 1994-08-25 1997-07-22 Agfa-Gevaert Aktiengesellschaft Polyacetylene-containing mouldings
FR2729888A1 (fr) * 1995-01-26 1996-08-02 Atochem Elf Sa Materiau d'emballage comprenant une couche d'oxyde de silicium et une couche de polyolefine
EP0723860A1 (fr) * 1995-01-26 1996-07-31 Elf Atochem S.A. Matériau d'emballage comprenant une couche d'oxyde de silicium et une couche de polyoléfine
US5712041A (en) * 1995-01-26 1998-01-27 Elf Atochem S.A. Packaging material comprising a silicon oxide layer and a polyolefin layer
WO1997042029A1 (fr) * 1996-05-06 1997-11-13 Convenience Food Systems B.V. Feuilles d'arret multicouches scellables transparentes
WO1997047678A1 (fr) * 1996-06-12 1997-12-18 Hoechst Trespaphan Gmbh Procede d'application d'une couche de fond de revetements sur des articles de polyolefine
US5925428A (en) * 1996-06-12 1999-07-20 Hoechst Trespaphan Gmbh Vapor barrier coating for polymeric articles
US6013128A (en) * 1996-06-12 2000-01-11 Hoechst Trespaphan Gmbh Vapor barrier coating for polymeric articles
US6086991A (en) * 1996-06-12 2000-07-11 Hoechst Trespaphan Gmbh Method of priming poly(ethylene terephthalate) articles for coating
AU733291B2 (en) * 1996-06-12 2001-05-10 Trespaphan Gmbh Method of priming polyolefin articles for coating
US6254994B1 (en) 1996-06-12 2001-07-03 Hoechst Trespaphan Gmbh Method of priming polyolefin articles for coating
US6368677B2 (en) 1996-06-12 2002-04-09 Hoechst Trespaphan Gmbh Method of priming polyolefin articles for coating
CN1086398C (zh) * 1996-06-12 2002-06-19 赫彻斯特－特拉丝帕番有限公司 涂覆聚烯烃制件的打底方法
US6531197B2 (en) 1999-04-26 2003-03-11 Illinois Tool Works Desiccant barrier container
DE102007019994A1 (de) 2007-04-27 2008-10-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Transparente Barrierefolie und Verfahren zum Herstellen derselben
DE102008019665A1 (de) 2008-04-18 2009-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Transparentes Barriereschichtsystem

Also Published As

Publication number Publication date
DE3882001D1 (de) 1993-07-29
DE3882001T2 (de) 1993-09-30
KR890006386A (ko) 1989-06-13
EP0311432A3 (en) 1990-04-25
KR960000749B1 (ko) 1996-01-12
EP0311432B1 (fr) 1993-06-23
US5100720A (en) 1992-03-31

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